Manufacture of new derivatives of naphthoquinones



Patented Apr. 17, 1928.

UNITED STATES PATENT QFHQE.

ROBERT LANTZ, OF PARIS, AND ANDRE WAHL, OF ENGHIEN, FRANCE, ASSIGNORS F ONE-H.514! TO SOCIETE ANONYME DES MATIERES COLORANTES 8: PRODUITS CHI- MIQUES DE SAINT-DENIS, 0F PARIS, FRANCE.

'MANUFACTURE OF NEW DERIVATIVES OF NAPHTHOQUINONES.

No Drawing. Application filed January 21, 1926 In U. S. Patent application Serial No. 670,099, filed October 22, 1923, there is described the manufacture of a new series 0t naphtho-quinone derivatives of the general formula:

R1 NHRI These may be called 2-hydroxy-1z4-diaryliminonaphthoquinones or i-arylamino-larylimino-2-naphthoquinones, accordingly as the first or the second of the above formulae represents the constitution. In these formulae R and R may represent identical or diflerent aromatic radicals. 1n the aforesaid specification it has been pointed out I 1 m. 7 mm O NlEhR NHzR NHR! NHR It. was hoped that the same reaction might I NH:

+ 0! NHaR I 21320 OaNa 65 The most suitable oxidizing agent is atmospheric oxygen, or better pure oxygen, under pressure or not, but other oxidizing agents may be used.

It should be observed that aminonaphthol, '70 and its -sulphonic acid may be prepared from nitrosonaphthol, which is subjected to Serial No. 82,878, and in France January 21, 1925.

be realized in the case of the most simple members of the series, in which, R becomes hydrogen, but these compounds which would be represented by the formulae:

HR NR and would be called l-iminoA-arylimino-Q- naphthoquinone or 1-imino-2-oxy-4-aryliminonaphth'oquinone, are not known.

Their analogues, the 2-hydroXy-4-aryh imino-l-naphthoquinones, which diller from them only by substitution of O for NH, arev obtained by-the reaction between [3 naphthoquinone or its sulphonated'derivative and an aromatic amine, but the same process can not be used for making the imino-dcrivatives l'or neither iinino-naphthoquinone nor iminonaphthoquinone sulphonic acid is known.

According to the present invention it is possible under suitable conditions to realize simultaneously the oxidation and the condensation of the aminonaphthol .12, substituted or not in position 4 by a sulphonic group, with the primary aromatic amines.

The reaction may now be written as follows I on comm mo reducing agents. However, it is not necessary to first reduce the nitroso-naphthol to aminonaphthol 1.2 or to aminonaphtholsulphonic 1-2-4 so as to subsequently re-o'xidize these bodies in the presence of the primary aromatic amines; applicants have in fact found that the nitrosonaphthol 1.2 may be made to react directly upon the primary aromatic amines according to the formula bill The imino-2-hydroxy-2-arylimino-4-napl1- thoquinones thus made are yellow, more or are dissolved in 500 parts of water contain- 5 ing 5.8 parts of-sodium bicarbonate and while this solution is violently agitated in contact With air there are introduced gradually 7.2 parts of, 1:2:4-ami11onaphthol sulphonic acid. An insoluble yellow crystalline precipitate is speedily formed. It is 4 diamine'or the like issubstituted for the drained and washed and may be re-cryst'alliz'ed from alcohol. needles, grouped in dots, melts with decomposition, dissolves in concentrated sulphuric acid to an orange solution, is insoluble in water but soluble in dilute caustic alkalies.

If in this example the corresponding quantity of aniline, ortho-toluidine, .ortho anisidine, parachloraniline para-phenylenepara-toluidine there is obtained an analogous compound. Instead of Working in contact with air the operation may be conducted in a closed vessel in an atmosphere of oxygen.

Ewample 2-52 parts of 1:2:4-a-mino-- naphthol sulphonic acid, 14 parts of anhydrous sodium carbonate and 25 parts ofaniline are dissolved in 800 parts of Water. The cold solution is agitated and oxidized by' gradual addition of sodium hypochlorite until there is an excess of chlorine and the precipitate no longer increases. The latter 1 is drained and may be purified by solution in cold dilute caustic soda and immediate reprecipitation from the filtered solution, by

' tained by using sodium bicarbonate. The 1-imino-2-hydroxy- 4-phenyliminonaphthoquinone' thus obtained crystallizes from alcohol in brilliant orange plates. The same result is obsuch as ammonlum persulphate, or iodine dissolved in alkaline blcarbonate solution.

Examplev 3.'30 parts of nitros0-,8- naph-' thol are dissolved in 300 parts. of aniline and 30 parts of benzine. The whole is heat- It then formsyellow.

another oxidizing agent,

ed to boiling, which is continued for about 12 minutes. After cooling, the mass is left at rest for some" time. It consists of beautiful yellow plates which constitute the following compound: 7

biCuHs identical withthat described in Example 2, and shows the chemical properties and analysis of this body.

Analysis.

I i Calculated Found I01 Cm n ON! C 77,54 77,4 H 4,94 4,3 N 11,36 11,3

Example 4. -A mixture of 3.2 parts of 1.2 amino-naphthol 8 parts of anhydrous sodium carbonate, 3 parts of aniline and 400 parts of water is agitated in contact with air. From the first there is formed a yellowish product which after12 hours agitation assumes a darker color. It is drained, redissolved in cold-dilute soda solution and the solution is filtered and precipitated With bicarbonate of soda. The product crystallizes from alcohol in the form of beautiful precedingimino body.

yellow crystals of the l/Vhat We claim-is: 1. As new products, the derivatives of imino-1-hydroxy-2-naphthoquinone 'sponding to the general formula:

wherein R designates an aromatic radical.

new compounds of the derivatives of imino- 1-hydroxy-2naphthoquinone, corresponding to the general formula:

I OH

R. wherein R designatesan aromatic radical which consists in the simultaneous oxidizingof aminonaphtholsulphonic acid 1.2.4 in the presence of the primary aromatic amines-.

In testimony whereof we have signed thisv specification.

' ROBERT LANTZ.

2. The herein described manufacture or" 

